4-Nitroaniline
{{chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 477223057
| Name = 4-Nitroaniline
| ImageFileL1 = p-Nitroanilin.svg
| ImageSizeL1 = 65px
| ImageAltL1 = Skeletal formula of p-nitroaniline
| ImageFileR1 = 4-Nitroaniline-3D-balls.png
| ImageSizeR1 = 110
| ImageAltR1 = Ball-and-stick model of the p-nitroaniline molecule
| ImageFile3 = P-nitroanilin.jpg
| ImageSize3 =
| PIN = 4-Nitroaniline
| SystematicName = 4-Nitrobenzenamine
| OtherNames = p-Nitroaniline
1-Amino-4-nitrobenzene
p-Nitrophenylamine
|Section1={{Chembox Identifiers
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 1MRQ0QZG7G
| PubChem = 7475
| EC_number = 202-810-1
| RTECS = BY7000000
| UNNumber = 1661
| KEGG = C02126
| Gmelin = 27331
| Beilstein = 508690
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 13846959
| SMILES = c1cc(ccc1N)N(=O)=O
| InChI = 1/C6H6N2O2/c7-5-1-3-6(4-2-5)8(9)10/h1-4H,7H2
| InChIKey = TYMLOMAKGOJONV-UHFFFAOYAW
| StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChI = 1S/C6H6N2O2/c7-5-1-3-6(4-2-5)8(9)10/h1-4H,7H2
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = TYMLOMAKGOJONV-UHFFFAOYSA-N
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 17064
| ChEMBL_Ref = {{ebicite|changed|EBI}}
| ChEMBL = 14282
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 100-01-6
}}
|Section2={{Chembox Properties
| Formula = C6H6N2O2
| MolarMass = 138.12 g/mol
| Appearance = yellow or brown powder
| Odor = faint, ammonia-like
| Density = 1.437 g/ml, solid
| Solubility = 0.8 mg/ml at 18.5 °C (IPCS)
| MeltingPtC = 146 to 149
| MeltingPt_notes = (lit.)
| BoilingPtC = 332
| BoilingPt_notes =
| VaporPressure = 0.00002 mmHg (20°C)
| MagSus = −66.43·10−6 cm3/mol
}}
|Section7={{Chembox Hazards
| ExternalSDS = [http://hazard.com/msds/mf/baker/baker/files/n4170.htm JT Baker]
| MainHazards = Toxic
| NFPA-H = 2
| NFPA-F = 1
| NFPA-R = 0
| NFPA-S =
| GHSPictograms = {{GHS06}}{{GHS08}}
| GHSSignalWord = Warning
| HPhrases = {{H-phrases|301|311|331|373|412}}
| PPhrases = {{P-phrases|260|261|264|270|271|273|280|301+310|302+352|304+340|311|312|314|321|322|330|361|363|403+233|405|501}}
| FlashPtC = 199
| PEL = TWA 6 mg/m3 (1 ppm) [skin]{{PGCH|0449}}
| LD50 = 3249 mg/kg (rat, oral)
750 mg/kg (rat, oral)
450 mg/kg (guinea pig, oral)
810 mg/kg (mouse, oral){{IDLH|100016|p-Nitroaniline}}
}}
|Section8={{Chembox Related
| OtherCompounds = 2-Nitroaniline, 3-Nitroaniline
}}
}}
4-Nitroaniline, p-nitroaniline or 1-amino-4-nitrobenzene is an organic compound with the formula C6H6N2O2. A yellow solid, it is one of three isomers of nitroaniline. It is an intermediate in the production of dyes, antioxidants, pharmaceuticals, gasoline, gum inhibitors, poultry medicines, and as a corrosion inhibitor.
Synthesis
4-Nitroaniline is produced industrially via the amination of 4-nitrochlorobenzene:{{Cite book |last=Booth |first=Gerald |url=https://onlinelibrary.wiley.com/doi/book/10.1002/14356007 |title=Ullmann's Encyclopedia of Industrial Chemistry |date=2003-03-11 |publisher=Wiley |isbn=978-3-527-30385-4 |editor-last=Wiley-VCH |edition=1 |language=en |chapter=Nitro Compounds, Aromatic |doi=10.1002/14356007.a17_411 |chapter-url=https://onlinelibrary.wiley.com/doi/abs/10.1002/14356007.a17_411}}]
:ClC6H4NO2 + 2 NH3 → H2NC6H4NO2 + NH4Cl
Below is a laboratory synthesis of 4-nitroaniline from aniline. The key step in this reaction sequence is an electrophilic aromatic substitution to install the nitro group para to the amino group. The amino group can be easily protonated and become a meta director. Therefore, a protection of the acetyl group is required. After this reaction, a separation must be performed to remove 2-nitroaniline, which is also formed in a small amount during the reaction.{{Cite book |last1=Mohrig |first1=J.R. |title=Experimental Organic Chemistry |last2=Morrill |first2=T.C. |last3=Hammond |first3=C.N. |last4=Neckers |first4=D.C. |publisher=Freeman |year=1997 |location=New York, NY |pages=456–467 |chapter=Synthesis 5: Synthesis of the Dye Para Red from Aniline |access-date=2007-07-18 |chapter-url=http://web.centre.edu/muzyka/organic/lab/paraRed05.htm |archive-url=https://web.archive.org/web/20200915092617/http://web.centre.edu/muzyka/organic/lab/paraRed05.htm |archive-date=2020-09-15 |url-status=dead}}
Applications
4-Nitroaniline is mainly consumed industrially as a precursor to p-phenylenediamine, an important dye component. The reduction is effected using iron metal and by catalytic hydrogenation.
It is a starting material for the synthesis of Para Red, the first azo dye:{{Cite book |last=Williamson |first=Kenneth L. |url=https://archive.org/details/macroscalemicros00will_0 |title=Macroscale and Microscale Organic Experiments, Fourth Edition |publisher=Houghton-Mifflin |year=2002 |isbn=0-618-19702-8 |url-access=registration}}
It is also a precursor to 2,6-dichloro-4-nitroaniline, also used in dyes.
=Laboratory use=
Nitroaniline undergoes diazotization, which allows access to 1,4-dinitrobenzene{{Cite journal |last=Starkey |first=E. B. |year=1939 |title=p-DINITROBENZENE |url=http://orgsyn.org/demo.aspx?prep=CV2P0225 |journal=Organic Syntheses |volume=19 |page=40 |doi=10.15227/orgsyn.019.0040|url-access=subscription }} and nitrophenylarsonic acid.{{Cite journal |year=1946 |title=p-Nitrophenylarsonic Acid |url=http://orgsyn.org/demo.aspx?prep=CV3P0665 |journal=Organic Syntheses |volume=26 |page=60 |doi=10.15227/orgsyn.026.0060|first1=A. Wayne |last1=Ruddy |first2= Edgar B. |last2=Starkey
|url-access=subscription }} With phosgene, it converts to 4-nitrophenylisocyanate.{{Cite journal |last1=Shriner |first1=R. L. |last2=Horne |first2=W. H. |last3=Cox |first3=R. F. B. |year=1934 |title=p-NITROPHENYL ISOCYANATE |url=http://orgsyn.org/demo.aspx?prep=CV2P0453 |journal=Organic Syntheses |volume=14 |page=72 |doi=10.15227/orgsyn.014.0072|url-access=subscription }}
=Carbon snake demonstration=
When mixed with sulfuric acid and heated, it dehydrates and polymerizes explosively into a rigid foam. The exact composition of the foam is unclear, but the process is believed to involve acidic protonation as well as displacement of the amine group by a sulfonic acid moiety.{{Cite journal |last1=Poshkus |first1=A. C. |last2=Parker |first2=J. A. |year=1970 |title=Studies on nitroaniline–sulfuric acid compositions: Aphrogenic pyrostats |url=https://onlinelibrary.wiley.com/doi/10.1002/app.1970.070140813 |journal=Journal of Applied Polymer Science |volume=14 |issue=8 |pages=2049–2064 |doi=10.1002/app.1970.070140813|url-access=subscription }}
In Carbon snake demo, paranitroaniline can be used instead of sugar, if the experiment is allowed to proceed under an obligatory fumehood.{{Cite book |last1=Summerlin |first1=Lee R. |url=https://eric.ed.gov/?id=ED286722 |title=Chemical Demonstrations: A Sourcebook for Teachers Volume 1 |last2=Ealy |first2=James L. |publisher=American Chemical Society |year=1988 |isbn=978-0-841-21481-1 |edition=2nd |pages=171 |chapter=Experiment 100: Dehydration of p-Nitroaniline: Sanke and Puff}} With this method the reaction phase prior to the black snake's appearance is longer, but once complete, the black snake itself rises from the container very rapidly.{{Cite web |date=2013-06-06 |title=Carbon Snake: demonstrating the dehydration power of concentrated sulfuric acid |url=https://communities.acs.org/t5/Educators-and-Students/Carbon-Snake-demonstrating-the-dehydration-power-of-concentrated/td-p/7732 |access-date=2022-01-31 |website=communities.acs.org |language=en}} This reaction may cause an explosion if too much sulfuric acid is used.{{Citation |title=Making a carbon snake with P-Nitroaniline | date=7 April 2014 |url=https://www.youtube.com/watch?v=YKHUnHDphTc |access-date=2022-01-31 |language=en}}
Toxicity
The compound is toxic by way of inhalation, ingestion, and absorption, and should be handled with care. Its {{LD50}} in rats is 750.0 mg/kg when administered orally. 4-Nitroaniline is particularly harmful to all aquatic organisms, and can cause long-term damage to the environment if released as a pollutant.{{Cite web |date=December 18, 2020 |title=4-Nitroaniline |url=https://www.sigmaaldrich.com/SG/en/sds/aldrich/185310 |publisher=Sigma-Aldrich |location=St. Louis, Missouri}}
See also
References
External links
{{commons category}}
- [https://web.archive.org/web/20071011164242/http://ptcl.chem.ox.ac.uk/MSDS/NI/p-nitroaniline.html Safety (MSDS)data for p-nitroaniline]
- [http://hazard.com/msds/mf/baker/baker/files/n4170.htm MSDS Sheet for p-nitroaniline]
- [http://www.sigmaaldrich.com/catalog/search/ProductDetail/ALDRICH/185310 Sigma-Aldrich Catalog data]
- [https://www.cdc.gov/niosh/npg/npgd0449.html CDC - NIOSH Pocket Guide to Chemical Hazards]
{{DEFAULTSORT:Nitroaniline, 4-}}
Category:IARC Group 3 carcinogens